Condensed-phase system quantum time propagation

In a second example the discrete time-reversible propagation scheme for mixed quantum-classical dynamics is applied to simulate the photoexcitation process of I2 immersed in a solid Ar matrix initiated by a femtosecond laser puls. This system serves as a prototypical model in experiment and theory for the understanding of photoinduced condensed phase chemical reactions and the accompanied phenomena like the cage effect and vibrational energy relaxation. It turns out that the energy transfer between the quantum manifolds as well as the transfer from the quantum system to the classical one (and back) can be very well described within the mixed mode frame outlined above. [Pg.151]

Linearization methods start from a path integral representation of the forward and backward propagators in expressions for time correlation function, and combine them to describe the overall time evolution of the system in terms of a set of classical trajectories whose initial conditions are sampled from a quantity related to the Wigner transform of the quantum density operator. The linearized expression for a correlation function provides a powerful tool for describing systems in the condensed phase. The rapid decay of... [Pg.557]